Condensates of rosin with unsaturated carbocyclic compounds



Patented Nov. 28, 1950 UNITED sures PATENT OFF-ICE CONDENSATES OF ROSIN WITH UNSATU- RATED CARBOCYCLIC COMPOUNDS Alfred 1.. Rummelsburg, Wilmington, Del., usignor. to Hercules Powder Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application Mn 21, 1946. Serial No. 871,392

19 Claims. (Cl. 108-22'I) bodying characteristics. Polymerization of rosin has been one means practiced by the art to overcome such deficiencies. By polymerization of rosin some improvement has been obtained but products which would be entirely satisfactory from the standpoint of bodying and drying characteristics have not been produced by polymerization alone.

Now in accordance with this invention. it has been found that rosin may be condensed with unsaturated carbocyclic compounds to form novel resinous condensation products which may be esteriiled, the condensation products more particularly in the form of their esters exhibiting the desired improvement in bodying, drying, and flexibility characteristics when used in varnishes and other coating compositions.

More particularly, the condensation products of rosin with unsaturated carbocyclic compounds of this invention are resinous products obtained by condensing a rosin with an unsaturated carbo-' cyclic compound which is capable of self polyr'nerization to a hemicolloid with a condensation catalyst at temperatures within the range of the particular materials being condensed and The conditions for effecting the condensation of rosin with the unsaturated carbocyclic cornpounds are more specifically set forth in the following examples. Unless otherwise noted all weights are parts by weight.

trample 1 To a solution of 450 parts inhibitor-free styrene and 1560 parts Wood rosin dissolved in 2340 parts benzene was added boron trifluoride gas over a period of 0.75 hour with stirring fwhile maintainbenzene. and both benzene and the last of thexylene were removed by heating up to about C. at 15-25 mm. pressure. The rosin condensate thus freed of solvent amounted to 1976 parts by weight and had the following analysis: acid number 123. drop melting point 124 C. From the weight of the condensate. it is calculated thatthe rosin-styrene condensate contains about 0.8+ mole of styrene per mole of rosin.

Examples 2 to 16 were carried'out in a similar manner. The dataon the condensation and characteristics of the rosin condensates are set forth in Table I. The rosins used were pale wood other factors. 5 rosins.

Table I Resctants Reaction. Conditions Example Carbocyclie Compound Cwegght w I m w l ht w i ht i T in cye g e g e g me amperaclic Com Rosin Cataly Catalyst 5mm Solvent Minutes ture, o.

pound Styrene 450 l, 560 BFi 36 Benzene--. 2, 340 235 17-25 do 458 000 do 20 r 900 290 11-28 d 15 100 do 2 r o 150 105 30 do 69 100 do 3 ro 169 110 20-23 alpha-Methyl Styrene 300 do 7 d o 450 130 23-30 blorostyrene 37 76 do 3 r 113 120 24-30 alpha-Methyl-pam-Methyl Styren 94 250 do 7 d 375 90 24-30 Divinyl Benzene (40%) 500 1,504 do 15 -do 2,256 240 20-25 40 860 do 18 do 1, 290 240 25-30 Divinyl Benzene 30 200 211011." 6 Nsphtha. 100 240 130 do 44 240 H18 50 Benzene--- 360 20-29 Diisopropenyl Benzene 31 137 BF; 4 do 219 2530 Cyciopentadiene 112 600 do 12 do 900 240 20-25 111162 39 B. P. 114 C./ nun. up 32.5 100 do 2 do 150 240 20-30 15 Indene (40%) 385 700 n 14 n 1, 050 210 15-25 16. PhenylAeetylenc 20 70 .do 1.4 do 240 31-30 17 Styrene 91' 302 HF"... 18 do 303 240' 15-40 Table I-C'ontinued Products run I Carbocycli' I pl. weigh Acid 33 Unsa niil- Moiemlu Number able mm warm I 5 um i, 976 123 124 fin 1,043 89.5 135 n 114 187. 5 12) 8.1 412 A 11 St 3 12 ii? 3'2 588 ai ha-Met l yr n bychlorostyz 88 118 alYha-Methyi-para-Methyi Styrene 328 104 D vinyl Benzene (40%)-- i, 992 116 166. 5 3.8 1B 1 g e a 9 Di enzene fl (50%) 285 126 136 6. l Diisopropenyl B 166 128 129 6. 3 Oyciopcnt 710 134 129 4.8 .[ndene B. P. 114 QJlill mm. In 1.51: 134 116 146 8. 1 .'ndene( 908 123- 134 Phenyi Acetylen 90 101 126 14.6 iityrel'i I y 384 126. 6 i 120. 5 9. 2

The rosins which are used are those having ethylenic unsaturation, such as the natural rosins of the type of wood and gum rosin, and treated resins such as heat-bleached,heat-treated, and

The unsaturated carbocyclic compounds used are those which are capable of selfpolymerization to hemicolloids; i. e.-, to polymershaving at least to 100 units per polymer molecule. Carbocyclic compounds of this type and suitable for use'in this invention are compoundshaving a single *center or unsaturation such as styrene, alpha-methyl styrene, alpha-methyl-para-methyl styrene, dichlorostyre'nef indene, and phenyl acetylene; and compounds having at least; two centers of unsaturation such as divinyl benzene, diisopr'openyl generally higher melting than rosin and are believed to be true condensates as indicated by the low unsaponifiable content. The preferred products of this invention have an unsaponiflable content not substantially g eater and melting points substantially higher .than those of the rosin's from which they are made. -They are 5 weight of the alcohol is increased.

V The condensation products of rosin with unsaturated'carbocyclic compounds having a single center of unsaturation appear to be high molecular weight monocarboxylic acids containing benzene, cyclopentadiene,-; and mixtures of any 0 chiefly only one resin acid nucleus per molecule.

of'these compounds may be used. The molecular ratio of main to unsaturated carbocyclic compound in .the condensation,may vary from about-0.1 to 20. Any unreacted carbocyclic compound remaining may be-removed from the condensation product, as for example by distillation. Since a -oatalyst is;desired,-* any of the well: known condensation-catalysts maybeused such as the Friedel-Craifts type catalysts including borontrifluoridqcomplexes of boron trifluorlde with ethers and-organicaeids', halides of metals whose hydroxides .are I amphoteric, such as aluminum chloride, nine chloride, stannic chloride, titanium tetrachloride, etc., and mineral acid condensation catalysts, such as hydrofluoric acid, fluoboric acid, sulfuric acid, and phosphoric acid. The Friedel-Crafts type catalysts are preferred.

When a catalystis' used for-the condensation,

--a temperature range varying from as low as e a wa 8 as 0."? Ordinarily temperatures from abo about 60? C. are preferred with boron trifluoride C. may be used.

catalysts whfle with zinc chloride "the preferred itemperature range is 100 C. to 140 C.

j Inert solvents may be used to improve the 55 fluidity of' the reactants and to facilitate 'dislpersion oi the catalyst. v Satisfactory solvents are aromatic solvents such as benzene, xylene,.and

the like; hydrocarbonfsolvents such as cyclojhexane and benzene hydrocarbons, and halo- 7 genated solvents such as carbon tetrachlorideand "ethylene dichloride The rosin condensates of thisinvention stabilized resinous materials having decreased These acids may be mixtures of condensation products wherein one or more molecule of unsaturated carbocyclic compound-for example, is condensed with a single resin acid molecule.

The condensation products 0! rosin with unsaturated carbocyclic compounds having more than one center of unsaturation in the molecule appear-to contain polybasic acids wherein more than one resin acid nucleus has been condensed with the polyunsaturated carboeyclic compound.

Moreoventhe condensate appears to be a mixture of monocarboxylic acids and polycarboxylic acids depending upon the conditions used in effecting the condensation. An example of a 50 condensate rich in dibasic acids and the conditions for its preparation are set forth in Table 1, Example 8. The preferred condensates of this invention are those having an average molecular weight -between about 350 and 1000. The con- ,W densation products containing various ratios of, ut'O" Cxto resin acid to carbocyclic compound are prepared by varying the amount of unsaturated carbocyclic compound added in the condensation and by controlling the rate of condensation.

The esters of the condensation products of rosin with unsaturated carbocyclic compounds may be prepared by heating with-the desired alcohol at temperatures within the range of about 200 C.

to. about 350 C. with or without catalysts such "as zinc and calcium salts; 4

- "The method of preparing'theesters of the condensation products of rosin, with unsaturated carbocyclic compounds of this invention and the properties of the esters so produced are illustendency to absorb oxygen. Moreover, they are trated by the examples of Table II.

TABLE II Ester Preparation Ester G 1 a Tem- Varnish Ex 1 Wt. w c Wt. M R w Wt. uu- Time- Acid Drop No. Calcium 01 e seedOll Num- Meltin Acetate FattyAcids t g' bot Point Styrene-Rosin 1 000 50.2 125 mm 10.8 131.11

(in 2 000 sea 14:; 200-210 11.3 141 Indene-Rosin 14 000 60.8 14 200-210 10.3 141 Divi ylBenzene-Rosi g x g: 7 345 3 $323 7 .g-.

n an 1.1 400 37.5 7 280-295 22.5 110 Cyclopantadiene-Rosiu- 13 600 66.2 13 200-270 151 Varnish Preparation e Condensate Bodying "W Ew't za Lg i seea 33$ (Llama) s 1' ns Castor Qll 85F Styrene-Rosin 200 400 I00 0 Indene-Rosin Divgiyl Benzene-Rosin Cyclopentadiene-Rosin.

The alcohols which may be used to esteri fy the condensation products of rosin with the unsaturated carbocyclic compounds are the monohydric alcohols such as methyl alcohol, ethyl a1- cohol, propyl alcohol, etc., and the polyhydric alcohols such as glycol, glycerin, pentaerythritol, dipentaerythritol, sorbitol, mannitol, propylene glycol, polyethylene glycols, trimethylene glycol. and diglycerol. The polyhydric alcohol esters are hard resinous materials having decreased tendency to absorb oxygen and having in general melting points higher than the corresponding rosin esters. If desired esters may likewise be prepared directly by use of a rosin ester in the condensation reaction. Mixed esters of the condensation products may be produced by esteriflcation in admixture with other acidic materials as drying oil fatty acids.

varnishes may be produced from the condensation products of this invention or their esters by customary varnishmaking technique with use Of any of the well-known drying oils such as linseed oil, tung oil, dehydrated castor oil, soya oil, fish oil, sunflower seed oil, rapeseed oil, perilla oil, oiticica oil, hemp seed oil, and dissolving in a solvent. Driers are preferably added. A varnish prepared from the ester of a condensation product of a rosin with an unsaturated carbocyclic compound of this invention may be carried out as follows: 200 parts glycerin ester of a styrene-rosin condensation product (Ester N0. 1,. Table II) was dissolved in 400 parts Z3 (Gardner-Holdt viscosity) linseed oil and heated rapidly to 585 F. at which temperature the cooking was continued for 100 minutes. This varnish cook was then diluted with mineral spirits to a concentration of 50% and 0.5% lead and 0.07 cobalt were added as naphthenates. The viscosity of the resulting varnish was 1.25 poises. This varnish as well as those whose preparation is set forth in Table II showed fast drying characteristics together with excellent flexibility and excellent water and alkali resistance.

The compositions of this invention can thus be made into oleoresinous varnishes having bodying characteristics and drying characteristics superior to those prepared from rosin or polymerized rosin and whose varnish films have greater water resistance, flexibility, and stability toward oxidation.

What I claim and desire to protect by Letters Patent is:

1. A new composition of matter comprising a material of the group consisting of a resinous product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with an unsaturated carbocyclic hydrocarbon having a single center of unsaturation and being capable of self-polymerization to a hemicolloid and aliphatic esters of said resinous product, the molar ratio of rosin to carbocyclic hydrocarbon in the condensation product being from about 0.1 to 20.

2. A new composition of matter comprising a resinous product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with an unsaturated carbocyclic hydrocarbon having a, single center of unsaturation and being capable of self-polymerization to a hemicolloid, the molar ratio of rosin to carbocyclic hydrocarbon in the condensation product being from about 0.1 to 20.

3. A new composition of matter comprising a resinous product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with styrene, the molar ratio of rosin to styrene in the condensation product being from about 0.1 to 20.

4. A new composition of matter comprising a material of the group consisting of a resinous product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with styrene and aliphatic esters of said resinous product, the molar ratio of rosin to styrene in the condensation product being from about 0.1 to 20.

5. A new composition of matter comprising a material of the group consisting of a resinous product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with a-methyl styrene and aliphatic esters of said resinous product, the molar ratio of rosin to a-methyl styrene in the condensation product being from about 0.1 to 20.

asaamo 8. A new composition of matter comprising a material of the group consisting 01 a resinous product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with a-methyl-p-methyl styrene and aliphatic esters of said resinous product, the molar ratio oi rosin to a-methyl-p-methyl styrene in the condensation product being from about 0.1 to 20.

7. A new composition of matter comprising a material of the group consisting of a resinous Product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with indene and aliphatic esters of said resinous product, the molar ratio of main to indene in the condensation product being from about 0.1 to 20.

8. A new composition of matter comprising a resinous ester of an aliphatic alcohol and a product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with styrene, the molar ratio of rosin to styrgne in the condensate being from about 0.1 to 2 9. A new composition of matter comprising a resinous ester or an aliphatic alcohol and a product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with a-methyl styrene, the molar ratio oi rosin to a-methyl styrene in the condensate being from about 0.1 to 20.

10. A new composition of matter comprising a resinous ester oi an aliphatic alcohol and a product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with a-methyl-p-methyl styrene, the molar ratio oi rosin to a-methyl-p-methyl styrene in the condensate being from about 0.1 to 20.

11. A new composition of matter comprising a resinous ester of an aliphatic alcohol and a product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with indene, the molar ratio of rosin to indene in the condensate being from about 0.1 to 20.

12. A coating composition comprising a resinous material selected from the group consisting of a resinous product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with an unsaturated carbocyclic hydrocarbon having a single center of unsaturation and being capable of self-polymerization to a hemicolloid and aliphatic polyhydric alcohol esters of said resinous product, the molar ratio of rosin to said carbocyclic hydrocarbon in the condensate being from about 0.1 to and a volatile petroleum hydrocarbon solvent in an amount suflicient to yield a readily flowing mixture capable of application in a thin film.

13. A coating composition comprising a resinous material selected from the group consisting of a resinous product of carbon-carbon condensation in the presence of an acid-acting condensation catalyst of rosin with a unsaturated carbocyclic hydrocarbon having a single center of 8 unsaturation and being capable of self-polymerization to a hemicolloid and aliphatic polyhydric alcohol esters of said resinous product, the molar ratio of rosin to said carbocyclic hydrocarbon in the condensate being from about 0.1 to 20; a drying oil; and a volatile petroleum hydrocarbon solvent in an amount sumcient to yield a readily flowing mixture capable of application in a thin film.

14. The method 0! producing a stabilized resinous material which comprises condensing one molar portion rosin with 0.1 to 20 molar portions unsaturated carbocyciic hydrocarbon having a single center of unsaturation and being capable of sell-polymerization to a hemioolloid. at a temperature within the range of about --50 ,C. to about C. in the presence oi an acid-acting condensation catalyst. v

15. The method of producing a stabilized resinous 'material which comprises condensing one molar portion rosin with 0.1 to 20 molar portions styrene at a temperature within the range of about 50 C. to about 150 C. in the presence of an acid-acting condensation catalyst.

16. The method of producing a stabilized resinous material which comprises condensing one molar portion rosin with 0.1 to 20 molar portions a-methyl styrene at a temperature within the range oi. about 50 C. to about 150 C. in the presence 0! an acid-acting condensation catalyst.

17. The method of producing a stabilized resinous material which comprises condensing one molar portion rosin with 0.1 to 20 molar portions e-methyl-p-methyl styrene at a temperature within the range of about 50 to about 150 C. in the presence or an acid-acting condensation catalyst.

18. The method of producing a stabilized resinous material which comprises condensing one molar portion rosin with 0.1 to 20 molar portions indene at a temperature within the range 01 about 50 C. to about 150 C. in the presence or an acid-acting condensation catalyst.

19. The method of producing a stabilized resinous material which comprises condensing one molar portion rosin with 0.1 to 20 molar portions phenyl acetylene at a temperature within the range or about -50 C. to about 150 C. in the presence of an acid-acting condensation catalyst. v

ALFRED L. RUMIMEIBBURG.

REFERENCES CITED The following references are of record in the tile of this patent:

UNITED STATES PATENTS Number Name Date 1,942,531 Barrett Jan. 9, 1934 1,975,959 Lawson et al Oct. 9. 1934 2,129,478 Rohm Sept. 6, 1938 2,251,806 Rust et al. Aug. 5, 1941 2,340,043 Clare Jan. 25, 1944 2,354,776 Rummelsburg Aug. 1. 1944 2,395,452 Bruson Feb. 26, 1946 2,488,770 Morris et al. May 3, 194 9 Certificate of Correction 5 Patent No. 2,532,120 I November 28, 1950 ALFRED L. RUMMELSBURG It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 5, line 65, for 0.07 read 0.07%;

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Oflice. Signed and sealed this 23rd day of January, A. D. 1951.

THOMAS F. MURPHY,

Assistant Uommissz'oner of Patents. 

1. A NEW COMPOSITION OF MATTER COMPRISING A MATERIAL OF THE GROUP CONSISTING OF A RESINOUS PRODUCT OF CARBON-CARBON CONDENSATION IN THE PRESENCE OF AN ACID-ACTING CONDENSATION CATALYST OF ROSIN WITH AN UNSATURATED CARBOCYLIC HYDROCARBON HAVING A SINGLE CENTER OF UNSATURATION AND BEING CAPABLE OF SELF-POLYMERIZATION TO A HEMICOLLOID AND ALIPHATIC ESTERS OF SAID RESINOUS PRODUCT, THE MOLAR RATIO OF ROSIN TO CARBOCYCLIC HYDROCARBON IN THE CONDENSATION PRODUCT BEING FROM ABOUT 0.1 TO
 20. 12. A COATING COMPOSITION COMPRISING A RESINOUS MATERIAL SELECTED FROM THE GROUP CONSISTING OF A RESINOUS PRODUCT OF CARBON-CARBON CONDENSATION IN THE PRESENCE OF AN ACID-ACTING CONDENSATION CATALYST OF ROSIN WITH AN UNSATURATED CARBOCYCLIC HYDROCARBON HAVING A SINGLE CENTER OF UNSATURATION AND BEING CAPABLE OF SELF-POLYMERIZATION TO A HEMICOLLOID AND ALIPHATIC POLYHYDRIC ALCOHOL ESTERS OF SAID RESINOUS PRODUCT, THE MOLAR RATIO OF ROSIN TO SAID CARBOCYCLIC HYDROCARBON IN THE CONDENSATE BEING FROM ABOUT 0.1 TO 20; AND A VOLATILE PETROLEUM HYDROCARBON SOLVENT IN AN AMOUNT SUFFICIENT TO YIELD A READILY FLOWING MIXTURE CAPABLE OF APPLICATION IN A THIN FILM. 